U.S. patent number 7,425,404 [Application Number 11/206,220] was granted by the patent office on 2008-09-16 for chemical amplification resist composition and pattern-forming method using the same.
This patent grant is currently assigned to FUJIFILM Corporation. Invention is credited to Hyou Takahashi, Shinji Tarutani, Kenji Wada.
United States Patent |
7,425,404 |
Tarutani , et al. |
September 16, 2008 |
Chemical amplification resist composition and pattern-forming
method using the same
Abstract
A chemical amplification resist composition comprising (A) a
resin increasing the solubility in an alkali developer by the
action of an acid, (B) a compound capable of generating an acid
upon irradiation with actinic ray or radiation, (C) a compound
having a fluorine atom and a hydroxyl group, and a pKa value of
from 4 to 15, and (D) a solvent, and a pattern-forming method using
the same.
Inventors: |
Tarutani; Shinji (Shizuoka,
JP), Takahashi; Hyou (Shizuoka, JP), Wada;
Kenji (Shizuoka, JP) |
Assignee: |
FUJIFILM Corporation (Tokyo,
JP)
|
Family
ID: |
35455982 |
Appl.
No.: |
11/206,220 |
Filed: |
August 18, 2005 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20060040208 A1 |
Feb 23, 2006 |
|
Foreign Application Priority Data
|
|
|
|
|
Aug 18, 2004 [JP] |
|
|
P.2004-238040 |
|
Current U.S.
Class: |
430/287.1;
430/270.1; 430/326 |
Current CPC
Class: |
G03F
7/0045 (20130101); G03F 7/0392 (20130101); G03F
7/0046 (20130101) |
Current International
Class: |
G03F
7/039 (20060101); G03F 7/038 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
0 445 058 |
|
Sep 1991 |
|
EP |
|
1 275 666 |
|
Jan 2003 |
|
EP |
|
1 505 440 |
|
Feb 2005 |
|
EP |
|
4-217251 |
|
Aug 1992 |
|
JP |
|
9-185158 |
|
Jul 1997 |
|
JP |
|
2003-156845 |
|
May 2003 |
|
JP |
|
2003-270791 |
|
Sep 2003 |
|
JP |
|
2003-287890 |
|
Oct 2003 |
|
JP |
|
WO 02/31595 |
|
Apr 2002 |
|
WO |
|
Other References
English translation of JP, 2003-287890, A (2003) from machine
translation from AIPN Japan Patent Office Natinal center for
Industrial Property Information and Training, generated Jul. 10,
2007, 17 pages. cited by examiner .
Ferreira et al "Choice of amines as stabilizers for chemically
amplifted resist systems", Proceedings of SPIE, vol. 333, Advances
in Resist Technology and Processing XV, WIII Conely, Ed, Jun. 1998,
pp. 236-244. cited by examiner .
Hamad et al, "Fluorinated dissolution inhibiotrs for 157 nm
lithography", Proceedings of SPIE vol. 4690, Advances in Resist
TEchnology and Processing XIX, Fedynyshyn, ed, Jul. 2002, pp.
477-485. cited by examiner .
Extended European Search Report dated Mar. 19, 2008. cited by
other.
|
Primary Examiner: Hamilton; Cynthia
Attorney, Agent or Firm: Sughrue Mion, PLLC
Claims
What is claimed is:
1. A chemical amplification resist composition comprising: (A) a
resin increasing the solubility in an alkali developer by the
action of an acid; (B) a compound capable of generating an acid
upon irradiation with actinic ray or radiation; (C) a compound
having a fluorine atom and a hydroxyl group, and a pKa value of
from 4 to 15; and (D) a solvent, wherein compound (C) includes (Ca)
a compound represented by the following formula (FAD-I) or
(FAD-III): ##STR00057## wherein R.sub.a101, R.sub.a102, R.sub.a103
and R.sub.a104 each represents a hydrogen atom, an alkyl group, an
alicylic alkyl group, an alkoxyl group, an acyl group or an acyloxy
group; A.sub.a101 represents a perfluoroalkylene group or a
perfluorocycloalkylene group; A.sub.a102 represents a single bond
or a divalent organic group; and R.sub.a106 represents a fluorine
atom or a perfluoroalkyl group, in which a plurality of R.sub.a106
each may be the same or different.
2. The chemical amplification resist composition as claimed in
claim 1, wherein the compound (Ca) is a compound represented by the
following formula (FAD-Ia): HO--CH.sub.2-A.sub.a101-CH.sub.2--OH
(FAD-Ia) wherein A.sub.a101 represents a perfluoroalkylene group or
a perfluorocycloalkylene group.
3. The chemical amplification resist composition as claimed in
claim 1, wherein the content of the component (C) in the solids
content of the chemical amplification resist composition is from
0.1 to 10 mass %.
4. The chemical amplification resist composition as claimed in
claim 1, wherein the resin (A) has at least one repeating unit
selected from the group consisting of a repeating unit having a
partial structure containing alicyclic hydrocarbon represented by
the following formula (pI), (pII), (pIII), (pIV), (pV) or (pVI),
and a repeating unit represented by the following formula (II-AB):
##STR00058## wherein R.sub.11 represents an alkyl group; Z
represents an atomic group necessary to form an alicyclic
hydrocarbon group together with a carbon atom; R.sub.12, R.sub.13,
R.sub.14, R.sub.15 and R.sub.16 each represents an alkyl group or
an alicyclic hydrocarbon group, provided that at least one of
R.sub.12 to R.sub.14, or either R.sub.15 or R.sub.16, represents an
alicyclic hydrocarbon group; R.sub.17, R.sub.18, R.sub.19, R.sub.20
and R.sub.21 each represents a hydrogen atom, an alkyl group or an
alicyclic hydrocarbon group, provided that at least one of R.sub.17
to R.sub.21 represents an alicyclic hydrocarbon group, and either
R.sub.19 or R.sub.21 represents an alkyl group or an alicyclic
hydrocarbon group; R.sub.22, R.sub.23, R.sub.24 and R.sub.25 each
represents an alkyl group or an alicyclic hydrocarbon group,
provided that at least one of R.sub.22 to R.sub.25 represents an
alicyclic hydrocarbon group, and R.sub.23 and R.sub.24 may be
bonded to each other to form a ring; ##STR00059## wherein R.sub.11
' and R.sub.12' each represents a hydrogen atom, a cyano group, a
halogen atom or an alkyl group; and Z' represents an atomic group
to form an alicyclic structure together with the bonded two carbon
atoms (C--C).
5. The chemical amplification resist composition as claimed in
claim 1, wherein the solvent (D) is a single solvent of alkyl
lactate or propylene glycol monoalkyl ether carboxylate, or a mixed
solvent containing at least two solvents selected from the group
consisting of propylene glycol monoalkyl ether carboxylate,
propylene glycol monoalkyl ether, cyclohexanone, and alkyl
lactate.
6. The chemical amplification resist composition as claimed in
claim 1, which further contains a nitrogen-containing basic
compound.
7. The chemical amplification resist composition as claimed in
claim 1, which further contains a surfactant containing at least
one of a fluorine atom and a silicon atom.
8. A pattern-forming method comprising; forming a resist film with
the chemical amplification resist composition as claimed in claim
1; and exposing and developing the resist film.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a chemical amplification resist
composition for use in manufacturing processes of semiconductor
devices, such as lithographic printing plate and IC, manufacture of
circuit substrates of liquid crystals, thermal heads and the like,
and other photo-fabrication processes, and also the invention
relates to a pattern-forming process using the same. In particular,
the invention relates to a chemical amplification resist
composition that functions by high energy radiation such as far
ultraviolet rays (including excimer lasers), electron beams, X-rays
or radiant rays, suitable for the manufacture of a semiconductor
integrated circuit, and the invention also relates to a
pattern-forming process using the same.
2. Background Art
In the manufacturing process of semiconductor devices such as IC
and LSI, fine processing by lithography using photo-resist
compositions has been conventionally performed. In recent years,
with the increment of integration of integrated circuits, ultrafine
pattern formation of the level of a sub-micron and quarter-micron
has come to be required. Under such a circumstance, the exposure
wavelengths show a tendency to be shortening, such as from g-ray to
i-ray, further to KrF excimer laser ray. Nowadays, lithography
using excimer laser rays is an important processing technique in
this field, and chemical amplification resists are adopted as the
resists suitable for such an excimer laser lithography process.
Chemical amplification resist compositions are materials that form
a pattern on a substrate by generating an acid upon irradiation
with radiation such as far ultraviolet rays on the exposed area,
and making difference in solubility in a developing solution of the
exposed area and unexposed area with the actinic radiation.
Chemical amplification resist compositions are advantageous in that
they have high sensitivity and high resolution, and they can form
an image with a compound capable of generating an acid (hereinafter
referred to as "a photo-acid generator") by irradiation with a
small quantity of radiation.
The above chemical amplification resist compositions can be
classified broadly into (a) s three-component system comprising an
alkali-soluble resin, a photo-acid generator, and a compound having
an acid-decomposable group that inhibits dissolution of an
alkali-soluble resin, (b) a two-component system comprising a resin
having a group decomposable by the reaction with an acid and
becoming alkali-soluble, and a photo-acid generator, and (c) a
hybrid system comprising a resin having a group decomposable by the
reaction with an acid and becoming alkali-soluble, a low molecular
weight dissolution-inhibiting compound having an acid-decomposable
group, and a photo-acid generator. In every positive chemical
amplification resist of these two-component system, three-component
system and hybrid system, a resist pattern is formed by the
development after heat treatment via an acid generated from
photo-acid generator upon exposure.
In lithography using chemical amplification resists, photo-resists
are generally required to be excellent in various characteristics,
e.g., sensitivity, resolution, profile, a coating property, heat
resistance, dry etching resistance, adhesion, substrate dependency,
stability resisting to environmental fluctuations (e.g.,
dimensional stability of a resist due to the fluctuation of lying
time), and focal depth (e.g., a pattern-forming property to focal
deviation at the time of irradiation with radiation), and various
contrivances of the improvement of performances by means of
additives are disclosed.
For example, the addition of an aromatic hydroxyl compound to a
chemical amplification resist composition for the increment of
sensitivity is disclosed in patent literature 1 (JP-A-4-217251 (the
term "JP-A" as used herein refers to an "unexamined published
Japanese patent application").
A trial of the addition of a compound having a fluorine atom in the
molecule to a chemical amplification resist composition for the
purpose of lessening the problem of development defect is disclosed
in patent literature 2 (JP-A-2003-156845).
The addition of a specific alcohol to a chemical amplification
resist composition for the improvement of the reproducibility and
stability of a pattern is disclosed in patent literature 3
(JP-A-9-185158).
Further, the addition of a chain-like compound having three or more
hydroxyl groups or substituted hydroxyl groups to a chemical
amplification resist composition for the improvement of line edge
roughness to thereby prevent the collapse of a pattern is disclosed
in patent literature 4 (JP-A-2003-270791).
However, even with these techniques, it is difficult to obtain a
chemical amplification resist composition that satisfies at the
same time the three points of capable of forming a good pattern
profile, being hardly accompanied by development defect and capable
of preventing pattern collapse.
SUMMARY OF THE INVENTION
An object of the invention is to provide a chemical amplification
resist composition that is improved in development defect, capable
of forming an excellent resist pattern profile, and capable of
preventing pattern collapse, and also relates to a pattern-forming
method using the same.
As a result of eager examination of the constitutional materials of
chemical amplification resist composition by the present inventors,
it was found that the above objects can be attained with a compound
containing a specific fluorine atom, thus the invention was
accomplished. That is, the above objects can be achieved by the
following constitution.
1. A chemical amplification resist composition comprising: (A) a
resin increasing the solubility in an alkali developer by the
action of an acid; (B) a compound capable of generating an acid
upon irradiation with actinic ray or radiation; (C) a compound
having a fluorine atom and a hydroxyl group, and a pKa value of
from 4 to 15; and (D) a solvent.
2. The chemical amplification resist composition as described in
the item 1, wherein the compound (C) includes (Ca) a compound
represented by the following formula (FAD-I), (FAD-II) or
(FAD-III):
##STR00001##
wherein R.sub.a101, R.sub.a102, R.sub.a103 and R.sub.a104 each
represents a hydrogen atom, an alkyl group, an alicyclic alkyl
group, an alkoxyl group, an acyl group or an acyloxy group;
A.sub.a101, represents a perfluoroalkylene group or a
perfluorocycloalkylene group;
R.sub.a105 represents a fluorine atom or a perfluoroalkyl group, in
which a plurality of R.sub.a105 each may be the same or
different;
n represents 1 or 2, and n+m=6;
A.sub.a102 represents a single bond or a divalent organic group;
and
R.sub.a106 represents a fluorine atom or a perfluoroalkyl group, in
which a plurality of R.sub.a106 each may be the same or
different.
3. The chemical amplification resist composition as described in
the item 2, wherein the compound (Ca) is a compound represented by
the following formula (FAD-Ia):
HO--CH.sub.2-A.sub.a101-CH.sub.2--OH (FAD-Ia) wherein A.sub.a101
represents a perfluoroalkylene group or a perfluorocycloalkylene
group.
4. The chemical amplification resist composition as described in
the item 1 or 2, wherein the content of the component (C) in the
solids content of the chemical amplification resist composition is
from 0.1 to 10 mass %.
5. The chemical amplification resist composition as described in
any one of the items 1 to 4, wherein the resin (A) has at least one
repeating unit selected from the group consisting of a repeating
unit having a partial structure containing alicyclic hydrocarbon
represented by the following formula (pI), (pII), (pIII), (pIV),
(pV) or (pVI), and a repeating unit represented by the following
formula (II-AB):
##STR00002##
wherein R.sub.11 represents an alkyl group; Z represents an atomic
group necessary to form an alicyclic hydrocarbon group together
with a carbon atom;
R.sub.12, R.sub.13, R.sub.14, R.sub.15 and R.sub.16 each represents
an alkyl group or an alicyclic hydrocarbon group, provided that at
least one of R.sub.12 to R.sub.14, or either R.sub.15 or R.sub.16,
represents an alicyclic hydrocarbon group;
R.sub.17, R.sub.18, R.sub.19, R.sub.20 and R.sub.21 each represents
a hydrogen atom, an alkyl group or an alicyclic hydrocarbon group,
provided that at least one of R.sub.17 to R.sub.21 represents an
alicyclic hydrocarbon group, and either R.sub.19 or R.sub.21
represents an alkyl group or an alicyclic hydrocarbon group;
R.sub.22, R.sub.23, R.sub.24 and R.sub.25 each represents an alkyl
group or an alicyclic hydrocarbon group, provided that at least one
of R.sub.22 to R.sub.25 represents an alicyclic hydrocarbon group,
and R.sub.23 and R.sub.24 may be bonded to each other to form a
ring;
##STR00003##
wherein R.sub.11' and R.sub.12' each represents a hydrogen atom, a
cyano group, a halogen atom or an alkyl group; and
Z' represents an atomic group to form an alicyclic structure
together with the bonded two carbon atoms (C--C).
6. The chemical amplification resist composition as described in
the item 1, wherein the solvent (D) is a single solvent of alkyl
lactate or propylene glycol monoalkyl ether carboxylate, or a mixed
solvent containing at least two solvents selected from the group
consisting of propylene glycol monoalkyl ether carboxylate,
propylene glycol monoalkyl ether, cyclohexanone, and alkyl
lactate.
7. The chemical amplification resist composition as described in
any one of the items 1 to 6, which further contains a
nitrogen-containing basic compound.
8. The chemical amplification resist composition as described in
any one of the items 1 to 7, which further contains a surfactant
containing at least one of a fluorine atom and a silicon atom.
9. A pattern-forming method comprising, forming a resist film with
the chemical amplification resist composition as described in the
items 1 to 8; and exposing and developing the resist film.
The invention can provide a chemical amplification resist
composition improved in the problem of development defect, from
which an excellent resist pattern profile can be obtained, and
capable of preventing the collapse of a pattern, and a
pattern-forming method using the same.
DETAILED DESCRIPTION OF THE INVENTION
The invention is described in detail below.
In the description of a group (an atomic group) in the
specification of the invention, the description not referring to
substitution or unsubstitution includes both a group not having a
substituent and a group having a substituent. For example, "an
alkyl group" includes not only an alkyl group having no substituent
(an unsubstituted alkyl group) but also an alkyl group having a
substituent (a substituted alkyl group.
[1] Resin Increasing the Solubility in an Alkali Developer by the
Action of an Acid (Component (A)):
A resin increasing the solubility in an alkali developer by the
action of an acid for use in a chemical amplification resist
composition in the invention is a resin having a group decomposable
by the action of an acid (hereinafter also referred to as "an
acid-decomposable group") on the main chain or side chain, or both
main and side chains, of the resin.
A preferred group decomposable by the action of an acid is a --COOH
group whose hydrogen atom is substituted with a group that is
desorbed by an acid.
Preferred acid-decomposable groups are a cumyl ester group, an enol
ester group, an acetal ester group, and a tertiary alkyl ester
group, and a more preferred group is a tertiary alkyl ester
group.
It is preferred for the resin of component (A) to have an alicyclic
hydrocarbon group.
As a resin having an alicyclic hydrocarbon group and increasing the
solubility in an alkali developer by the action of an acid
(hereinafter also referred to as "an alicyclic hydrocarbon-based
acid-decomposable resin"), it is preferred to have at least one
repeating unit selected from the group consisting of a repeating
unit having a partial structure containing alicyclic hydrocarbon
represented by any of the following formulae (pI) to (pVI), and a
repeating unit represented by the following formula (II-AB):
##STR00004##
In formulae (pI) to (pVI), R.sub.11 represents an alkyl group; Z
represents an atomic group necessary to form an alicyclic
hydrocarbon group together with a carbon atom;
R.sub.12, R.sub.13, R.sub.14, R.sub.15 and R.sub.16 each represents
an alkyl group or an alicyclic hydrocarbon group, provided that at
least one of R.sub.12 to R.sub.14, or either R.sub.15 or R.sub.16,
represents an alicyclic hydrocarbon group;
R.sub.17, R.sub.18, R.sub.19, R.sub.20 and R.sub.21 each represents
a hydrogen atom, an alkyl group or an alicyclic hydrocarbon group,
provided that at least one of R.sub.17 to R.sub.21 represents an
alicyclic hydrocarbon group, and either R.sub.19 or R.sub.21
represents an alkyl group or an alicyclic hydrocarbon group;
R.sub.22, R.sub.23, R.sub.24 and R.sub.25 each represents an alkyl
group or an alicyclic hydrocarbon group, provided that at least one
of R.sub.22 to R.sub.25 represents an alicyclic hydrocarbon group,
and R.sub.23 and R.sub.24 may be bonded to each other to form a
ring.
##STR00005##
In formula (II-AB), R.sub.11' and R.sub.12' each represents a
hydrogen atom, a cyano group, a halogen atom or an alkyl group;
and
Z' contains bonded two carbon atoms (C--C) and represents an atomic
group to form an alicyclic structure.
Formula (II-AB) is more preferably represented by the following
formula (II-A) or (II-B).
##STR00006##
In formulae (II-A) and (II-B), R.sub.13', R.sub.14', R.sub.15', and
R.sub.16' each represents a hydrogen atom, a halogen atom, a cyano
group, --COOH, --COOR.sub.5, a group decomposable by the action of
an acid, --C(.dbd.O)--X-A'-R.sub.17', an alkyl group, or a cyclic
hydrocarbon group, and at least two of R.sub.13' to R.sub.16' may
be bonded to each other to form a ring; n represents 0 or 1;
R.sub.5 represents an alkyl group, a cyclic hydrocarbon group, or a
--Y group shown below;
X represents an oxygen atom, a sulfur atom, --NH--, --NHSO.sub.2--
or --NHSO.sub.2NH--;
A' represents a single bond or a divalent linking group;
R.sub.17' represents --COOH, --COOR.sub.5, --CN, a hydroxyl group,
an alkoxyl group, --CO--NH--R.sub.6, --CO--NH--SO.sub.2--R.sub.6,
or a --Y group shown below;
R.sub.6 represents an alkyl group or a cyclic hydrocarbon
group.
--Y group:
##STR00007##
In --Y group, R.sub.21' to R.sub.30' each represents a hydrogen
atom or an alkyl group;
a and b each represents 1 or 2.
In formulae (pI) to (pVI), the alkyl group represented by R.sub.11
to R.sub.25 may be a substituted or unsubstituted alkyl group,
preferably a straight chain or branched alkyl group having from 1
to 4 carbon atoms, e.g., a methyl group, an ethyl group, an
n-propyl group, an isopropyl group, an n-butyl group, an isobutyl
group, a sec-butyl group, a t-butyl group, etc.
As the substituents of the substituted alkyl group, an alkoxyl
group having from 1 to 4 carbon atoms, a halogen atom (a fluorine
atom, a chlorine ion, a bromine ion, an iodine ion), an acyl group,
an acyloxy group, a cyano group, a hydroxyl group, a carboxyl
group, an alkoxycarbonyl group, and a nitro group can be
exemplified.
The alicyclic hydrocarbon groups represented by R.sub.12 to
R.sub.25, and the alicyclic hydrocarbon group formed by Z and a
carbon atom may be monocyclic or polycyclic. Specifically groups
having a monocyclic, bicyclic, tricyclic or tetracyclic structure
and having 5 or more carbon atoms can be exemplified. The carbon
atoms of the alicyclic hydrocarbon groups are preferably from 6 to
30, particularly preferably from 7 to 25. These alicyclic
hydrocarbon groups may have a substituent.
The examples of preferred alicyclic hydrocarbon groups include an
adamantyl group, a noradamantyl group, a decalin residue, a
tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl
group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a
cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group,
and more preferred groups are an adamantyl group, a decalin
residue, a norbornyl group, a cedrol group, a cyclohexyl group, a
cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a
cyclododecanyl group.
As the substituents of these alicyclic hydrocarbon groups, an alkyl
group, a halogen atom, a hydroxyl group, an alkoxyl group, a
carboxyl group, and an alkoxycarbonyl group are exemplified. As the
alkyl group, lower alkyl groups, e.g., a methyl group, an ethyl
group, a propyl group, an isopropyl group and a butyl group are
preferred, and a methyl group, an ethyl group, a propyl group and
an isopropyl group are more preferred. As the alkoxyl group,
alkoxyl groups having from 1 to 4 carbon atoms, e.g., a methoxy
group, an ethoxy group, a propoxy group and a butoxy group are
exemplified. These alkyl group and alkoxyl group may further have a
substituent, and as such further substituents of the alkyl and
alkoxyl groups, a hydroxyl group, a halogen atom and an alkoxyl
group can be exemplified.
The structures represented by formulae (pI) to (pVI) in the resin
of component (A) can be used for the protection of an
alkali-soluble group. As the alkali-soluble groups, various groups
known in the technical industry can be exemplified.
The specific examples of alkali-soluble groups are a carboxylic
acid group, a sulfonic acid group, a phenol group and a thiol
group, preferably a carboxylic acid group and a sulfonic acid
group.
As a preferred alkali-soluble group protected with the structure
represented by any of formulae (pI) to (pVI) in the resin of
component (A), a carboxyl group having a structure whose hydrogen
atom is substituted with a structure represented by any of formulae
(pI) to (pVI) is exemplified.
As a repeating unit having an alkali-soluble group protected with
the structure represented by any of formulae (pI) to (pVI), a
repeating unit represented by the following formula (pA) is
preferred.
##STR00008##
In formula (pA), R represents a hydrogen atom, a halogen atom, or a
substituted or unsubstituted, straight chain or branched alkyl
group having from 1 to 4 carbon atoms. A plurality of R may be the
same or different.
A represents a single group or a combination comprising two or more
groups selected from the group consisting of a single bond, an
alkylene group, an ether group, a thioether group, a carbonyl
group, an ester group, an amido group, a sulfonamido group, a
urethane group and a urea group. The alkylene group may have a
substituent.
Ra represents a group represented by any of formulae (pI) to
(pVI).
The repeating unit represented by (pA) is most preferably a
repeating unit by 2-alkyl-2-adamantyl(meth)acrylate,
dialkyl(1-adamantyl)methyl(meth)acrylate, or
1-ethyl-2-isopropyl-5-methyl-cyclohexyl (meth)acrylate.
The specific examples of the repeating units represented by formula
(pA) are shown below.
In the formulae, Rx represents H, CH.sub.3', CH.sub.2OH or
CF.sub.3.
##STR00009## ##STR00010## ##STR00011## ##STR00012##
In the above formula (II-AB), R.sub.11' and R.sub.12' each
represents a hydrogen atom, a cyano group, a halogen atom or an
alkyl group. Z' contains bonded two carbon atoms (C--C) and
represents an atomic group to form an alicyclic structure which may
have a substituent.
As the halogen atoms represented by R.sub.11' and R.sub.12', a
chlorine atom, a bromine atom, a fluorine atom and an iodine atom
are exemplified.
As the alkyl groups represented by R.sub.11' and R.sub.12',
straight chain or branched alkyl groups having from 1 to 10 carbon
atoms are preferred, more preferably straight chain or branched
alkyl groups having from 1 to 6 carbon atoms, and a methyl group,
an ethyl group, a propyl group, an isopropyl group, an n-butyl
group, an isobutyl group, a sec-butyl group and a t-butyl group are
more preferred.
The above alkyl groups may further have a substituent, and as such
substituents, a hydroxyl group, a halogen atom, a carboxyl group,
an alkoxyl group, an acyl group, a cyano group and an acyloxy group
are exemplified. As the halogen atom, a chlorine atom, a bromine
atom, a fluorine atom and an iodine atom are exemplified. As the
alkoxyl group, alkoxyl groups having from 1 to 4 carbon atoms,
e.g., a methoxy group, an ethoxy group, a propoxy group and a
butoxy group are exemplified. As the acyl group, a formyl group and
an acetyl group are exemplified. As the acyloxy group, an acetoxy
group is exemplified.
The atomic group represented by Z' for forming an alicyclic
structure is an atomic group for forming a repeating unit of
alicyclic hydrocarbon of a resin, which may have a substituent, and
an atomic group for forming a crosslinking alicyclic structure
forming a crosslinking alicyclic hydrocarbon repeating unit is
particularly preferred.
As the skeleton of alicyclic hydrocarbon formed, the same alicyclic
hydrocarbon groups as those represented by R.sub.11 to R.sub.25 in
formulae (pI) to (pVI) are exemplified.
The skeleton of alicyclic hydrocarbon may have a substituent, and
as the substituents, the groups represented by R.sub.13' to
R.sub.16' in formula (II-A) or (II-B) can be exemplified.
Of the repeating units having crosslinking alicyclic hydrocarbon,
repeating units represented by formula (II-A) or (II-B) are more
preferred.
In the alicyclic hydrocarbon-based acid-decomposable resin in the
invention, an acid-decomposable group may be contained in
--C(.dbd.O)--X-A'-R.sub.17', or may be contained as the substituent
of Z' in formula (II-AB).
The structure of an acid-decomposable group is represented by
formula --C(.dbd.O)--X.sub.1--R.sub.0.
In the above formula, R.sub.0 represents a tertiary alkyl group,
e.g., a t-butyl group or a t-amyl group, an isoboronyl group, a
1-alkoxyethyl group, e.g., a 1-ethoxyethyl group, a 1-butoxyethyl
group, a 1-isobutoxyethyl group, or a 1-cyclohexyloxyethyl group,
an alkoxymethyl group, e.g., a 1-methoxymethyl group or a
1-ethoxymethyl group, a 3-oxoalkyl group, a tetrahydropyranyl
group, a tetrahydrofuranyl group, a trialkylsilyl ester group, a
3-oxocyclohexyl ester group, a 2-methyl-2-adamantyl group, or a
mevalonic lactone residue. X.sub.1 has the same meaning as X
above.
As the halogen atoms represented by R.sub.13', R.sub.14', R.sub.15'
and R.sub.16' in formulae (II-A) and (II-B), a chlorine atom, a
bromine atom, a fluorine atom and an iodine atom can be
exemplified.
The alkyl groups represented by R.sub.5, R.sub.6, R.sub.13' to
R.sub.16', R.sub.21' to R.sub.30' are preferably straight chain or
branched alkyl groups having from 1 to 10 carbon atoms, more
preferably straight chain or branched alkyl groups having from 1 to
6 carbon atoms, and still more preferably a methyl group, an ethyl
group, a propyl group, an isopropyl group, an n-butyl group, an
isobutyl group, a sec-butyl group and t-butyl.
The cyclic hydrocarbon groups represented by R.sub.5, R.sub.6,
R.sub.13', R.sub.14', R.sub.15' and R.sub.16' are cyclic alkyl
groups and crosslinking hydrocarbon groups, e.g., a cyclopropyl
group, a cyclopentyl group, a cyclohexyl group, an adamantyl group,
a 2-methyl-2-adamantyl group, a norbornyl group, a boronyl group,
an isoboronyl group, a tricyclodecanyl group, a dicyclopentenyl
group, a norbornanepoxy group, a menthyl group, an isomenthyl
group, a neomenthyl group, and a tetracyclododecanyl group are
exemplified.
As the ring formed by bonding at least two of R.sup.13' to
R.sup.16', rings having from 5 to 12 carbon atoms, e.g.,
cyclopentene, cyclohexene, cycloheptane and cyclooctane can be
exemplified.
As the alkoxyl group represented by R.sub.17', alkoxyl groups
having from 1 to 4 carbon atoms, e.g., a methoxy group, an ethoxy
group, a propoxy group and a butoxy group can be exemplified.
As further substituents of the alkyl, cyclic hydrocarbon and
alkoxyl groups, a hydroxyl group, a halogen atom, a carboxyl group,
an alkoxyl group, an acyl group, a cyano group, an acyloxy group,
an alkyl group, and a cyclic hydrocarbon group can be exemplified.
As the halogen atom, a chlorine atom, a bromine atom, a fluorine
atom and an iodine atom can be exemplified. As the alkoxyl group,
alkoxyl groups having from 1 to 4 carbon atoms, e.g., a methoxy
group, an ethoxy group, a propoxy group and a butoxy group can be
exemplified. As the acyl group, a formyl group and an acetyl group
can be exemplified, and as the acyloxy group, an acetoxy group can
be exemplified.
As the alkyl and cyclic hydrocarbon groups, those described above
can be exemplified.
As the divalent linking group represented by A', a single group or
combinations comprising two or more groups selected from the group
consisting of an alkylene group, an ether group, a thioether group,
a carbonyl group, an ester group, an amido group, a sulfonamido
group, a urethane group and a urea group can be exemplified. The
alkylene group may further have a substituent.
In the alicyclic hydrocarbon-based acid-decomposable resin in the
invention, a group decomposable by the action of an acid can
contain at least one repeating unit of a repeating unit having a
partial structure containing alicyclic hydrocarbon represented by
any of formulae (pI) to (pVI), a repeating unit represented by
formula (II-AB), and a repeating unit of the later-described
copolymerization component.
The various substituents represented by R.sub.13' to R.sub.16' in
formulae (II-A) and (II-b) are also the substituents of the atomic
group for forming an alicyclic structure in formula (II-AB) or the
atomic group Z for forming a crosslinking alicyclic structure.
As the specific examples of the repeating units represented by
formulae (II-A) and (II-B), the following compounds are
exemplified, but the invention is not limited thereto.
##STR00013## ##STR00014## ##STR00015## ##STR00016##
It is preferred for the alicyclic hydrocarbon-based
acid-decomposable resin in the invention to have a lactone group,
more preferably have a repeating unit having a group having a
lactone structure represented by the following formula (Lc) or any
of formulae (V-1) to (V-7), and the group having a lactone
structure may be directly bonded to the main chain.
##STR00017##
In formula (Lc), R.sub.a1, R.sub.b1, R.sub.c1, R.sub.d1 and
R.sub.e1 each represents a hydrogen atom or an alkyl group; m and n
each represents an integer of from 0 to 3, and m+n is from 2 to
6.
In formulae (V-1) to (V-7), R.sub.1b, R.sub.2b, R.sub.3b, R.sub.4b
and R.sub.5b each represents a hydrogen atom, an alkyl group, a
cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, an
alkylsulfonyl-imino group, or an alkenyl group. Two of R.sub.1b to
R.sub.5b may be bonded to each other to form a ring.
In formulae (V-6) and (V-7), X.sub.L represents --O--, --S--,
--SO.sub.2-- or --N (R.sub.XL)--. R.sub.XL represents a hydrogen
atom, a hydroxyl group, an alkyl group or --OSO.sub.2--R.sub.XL1.
R.sub.XL1 represents an alkyl group, a cycloalkyl group, or a
camphor residue.
As the alkyl groups represented by R.sub.a1 to R.sub.e1 in formula
(Lc), and as the alkyl groups in the alkyl group, alkoxyl group,
alkoxycarbonyl group and alkylsulfonylimino group represented by
R.sub.1b to R.sub.5b in formulae (V-1) to (V-7), straight chain or
branched alkyl groups are exemplified, and these alkyl groups may
have a substituent.
As the repeating units having a group having a lactone structure
represented by formula (Lc) or any of formulae (V-1) to (V-7),
repeating units represented by formula (II-A) or (II-B) in which at
least one of R.sub.13' to R.sub.16' has a group represented by
formula (Lc) or any group represented by formulae (V-1) to (V-7)
(e.g., R.sub.5 of --COOR.sub.5 represents a group represented by
formula (Lc) or represented by any of formulae (V-1) to (V-7)), or
a repeating unit represented by the following formula (AI) can be
exemplified.
##STR00018##
In formula (AI), R.sub.b0 represents a hydrogen atom, a halogen
atom or an alkyl group. The alkyl group represented by R.sub.b0 is
preferably an alkyl group having from 1 to 4 carbon atoms. The
alkyl group represented by R.sub.b0 may further have a
substituent.
As the halogen atom represented by R.sub.b0, a fluorine atom, a
chlorine atom, a bromine atom or an iodine atom can be exemplified.
R.sub.b0 preferably represents a hydrogen atom.
A' represents a single bond, an ether group, an ester group, a
carbonyl group, an alkylene group, or a divalent group obtained by
combining these groups.
B.sub.2 represents a group represented by formula (Lc) or a group
represented by any of formulae (V-1) to (V-7).
The specific examples of repeating units having a lactone structure
are shown below, but the invention is not limited thereto.
(In the formulae, Rx represents H, CH.sub.3 or CF.sub.3.)
##STR00019## ##STR00020## ##STR00021##
(In the formulae, Rx represents H, CH.sub.3 or CF.sub.3.)
##STR00022## ##STR00023## ##STR00024##
(In the formulae, Rx represents H, CH.sub.3 or CF.sub.3.)
##STR00025## ##STR00026## ##STR00027##
The alicyclic hydrocarbon-based acid-decomposable resin in the
invention may have a repeating unit having a group represented by
the following formula (VII).
##STR00028##
In formula (VII), R.sub.2c, R.sub.3c, and R.sub.4c each represents
a hydrogen atom or a hydroxyl group, provided that at least one of
R.sub.2c to R.sub.4c represents a hydroxyl group.
The group represented by formula (VII) is preferably dihydroxy or
monohydroxy, preferably dihydroxy.
As the repeating unit having a group represented by formula (VII),
repeating units represented by formula (II-A) or (II-B) in which at
least one of R.sub.13' to R.sub.16' has a group represented by
formula (VII) (e.g., R.sub.5 of --COOR.sub.5 represents a group
represented by formula (VII)), or a repeating unit represented by
the following formula (AII) can be exemplified.
##STR00029##
In formula (AII), R.sub.1c represents a hydrogen atom or a methyl
group.
R.sub.2c, R.sub.3c and R.sub.4c each represents a hydrogen atom or
a hydroxyl group, provided that at least one of R.sub.2c to
R.sub.4c represents a hydroxyl group, preferably two of R.sub.2c to
R.sub.4c represent a hydroxyl group.
The specific examples of repeating units having the structure
represented by formula (AII) are shown below, but the invention is
not limited thereto.
##STR00030##
The alicyclic hydrocarbon-based acid-decomposable resin in the
invention may have a repeating unit represented by the following
formula (VIII).
##STR00031##
In formula (VIII), Z.sub.2 represents --O-- or --N(R.sub.41)--;
R.sub.41 represents a hydrogen atom, a hydroxyl group, an alkyl
group, or --OSO.sub.2--R.sub.42; R.sub.42 represents an alkyl
group, a cycloalkyl group or a camphor residue; the alkyl group may
have a substituent, e.g., a halogen atom.
As the specific examples of the repeating units represented by
formula (VIII), the following [I'-1] to [I'-7] are exemplified, but
the invention is not limited thereto.
##STR00032##
The alicyclic hydrocarbon-based acid-decomposable resin in the
invention can contain various repeating units other than the above
repeating units for the purpose of adjusting dry etching
resistance, aptitude for standard developing solutions, adhesion to
a substrate, resist profile, and further, generally necessary
characteristics such as resolution, heat resistance and
sensitivity.
As such repeating units, repeating units corresponding to the
monomers shown below can be exemplified, but the invention is not
limited thereto.
By containing various kinds of repeating units, fine adjustment of
performances required of the alicyclic hydrocarbon-based
acid-decomposable resins, in particular fine adjustment of the
following performances becomes possible, that is, (1) Solubility in
a coating solvent, (2) A film-forming property (a glass transition
point), (3) Alkali developability, (4) Decrease of layer thickness
(hydrophobic-hydrophilic property, selection of an alkali-soluble
group), (5) Adhesion of an unexposed area to a substrate, and (6)
Dry etching resistance.
The examples of such monomers include compounds having one addition
polymerizable unsaturated bond selected from acrylic esters,
methacrylic esters, acrylamides, methacryl-amides, allyl compounds,
vinyl ethers and vinyl esters.
In addition to the aforementioned compounds, addition polymerizable
unsaturated compounds copolymerizable with the monomers
corresponding to the above various repeating structural units may
be used for copolymerization.
In the alicyclic hydrocarbon-based acid-decomposable resin of the
invention, the molar ratio of the content of each repeating
structural unit is arbitrarily selected to adjust dry etching
resistance, aptitude for standard developing solutions, adhesion to
the substrates, and resist profile, in addition to these, to adjust
general requisite characteristics of resists, e.g., resolution,
heat resistance and sensitivity.
As preferred embodiments of the alicyclic hydrocarbon-based
acid-decomposable resin of the invention, the following resins can
be exemplified. (1) A resin having a repeating unit having a
partial structure containing alicyclic hydrocarbon represented by
any of formulae (pI) to (pVI) (a side chain type); (2) A resin
having a repeating unit represented by formula (II-AB) (a main
chain type); provided that the following is further exemplified as
embodiment (2): (3) A resin having a repeating unit represented by
formula (II-AB), a maleic acid derivative and (meth)acrylate
structure (a hybrid type).
The content of a repeating unit having an acid-decomposable croup
in the alicyclic hydrocarbon-based acid-decomposable resin is
preferably from 10 to 70 mol % in the total repeating structural
units, more preferably from 20 to 65 mol %, and still more
preferably from 25 to 60 mol %.
The content of a repeating unit having a partial structure
containing alicyclic hydrocarbon represented by any of formulae
(pI) to (pVI) in the alicyclic hydrocarbon-based acid-decomposable
resin is preferably from 20 to 70 mol % in the total repeating
structural units, more preferably from 24 to 65 mol %, and still
more preferably from 28 to 60 mol %.
The content of a repeating unit represented by formula (II-AB) in
the alicyclic hydrocarbon-based acid-decomposable resin is
preferably from 10 to 60 mol % in the total repeating structural
units, more preferably from 15 to 55 mol %, and still more
preferably from 20 to 50 mol %.
The content of the repeating structural units on the basis of the
monomers of further copolymerization components in the resin can
also be optionally set according to the desired resist
performances, and the content is generally preferably 99 mol % or
less to the total mol number of a repeating structural unit having
a partial structure containing the alicyclic hydrocarbon
represented by any of formulae (pI) to (pVI) and a repeating unit
represented by formula (II-AB), more preferably 90 mol % or less,
and still more preferably 80 mol % or less.
When the composition in the invention is for ArF exposure, it is
preferred that the resin does not have aromatic groups from the
aspect of the transparency to ArF rays.
The alicyclic hydrocarbon-based acid-decomposable resin of the
invention can be synthesized according to ordinary methods (e.g.,
radical polymerization). For example, as ordinary methods, a
monomer seed is put in a reaction vessel at a time or in parts
during the course of the reaction, and according to necessity the
monomer seed is dissolved in a reaction solvent such as cyclic
ethers, e.g., tetrahydrofuran or 1,4-dioxane, ketones, e.g., methyl
ethyl ketone, methyl isobutyl ketone or cyclohexanone, or the
later-described solvents capable of dissolving the composition of
the invention, e.g., propyelne glycol monomethyl ether acetate or
propyelne glycol monomethyl ether, to make the monomer homogeneous.
The solution is then heated, if necessary, under the inert gas
atmosphere such as nitrogen or argon, and polymerization is
initiated with commercially available radical polymerization
initiator (e.g., azo initiators, peroxide and the like). If
necessary, the initiator is further added at a time or in parts,
and after completion of the reaction, the reaction system is put
into a solvent, and a desired polymer is recovered as powder or
solid. The reaction concentration is 10 mass % or more, preferably
15 mass % or more, and more preferably 20 mass % or more. The
reaction temperature is from 10 to 150.degree. C., preferably from
30 to 130.degree. C., and more preferably from 50 to 100.degree.
C.
The repeating structural unit in the above specific example may be
used as one kind alone, or a plurality of repeating units may be
used as mixture.
Further, a resin may be used as one kind alone, or a plurality of
resins may be used in combination.
The weight average molecular weight of the resin in the invention
is preferably from 1,000 to 200,000 in polystyrene equivalent by
the GPC method, more preferably from 3,000 to 20,000. By bringing
the weight average molecular weight to the range of from 1,000 to
200,000, heat resistance, dry etching resistance, developability
and film-forming property are prevented from deteriorating.
The molecular weight distribution of the resin in the invention is
generally from 1 to 5, preferably from 1 to 4, and more preferably
from 1 to 3. By bringing the molecular weight distribution to the
range of from 1 to 5, deterioration of resolution and resist
configuration, chapping of the sidewall of a resist pattern, and
deterioration of roughness properties are prevented.
In the chemical amplification resist composition of the invention,
the blending amount of all the resins in the entire composition is
preferably from 40 to 99.99 mass % in all the solids content of the
resist, more preferably from 50 to 99.97 mass %.
[2] A Compound Capable of Generating an Acid Upon Irradiation with
Actinic Ray or Radiation (Component (B)):
The chemical amplification resist composition in the invention
contains a compound capable of generating an acid upon irradiation
with actinic ray or radiation. As such a photo-acid generator,
photo-polymerization initiators of photo-cationic polymerization,
photo-polymerization initiators of photo-radical polymerization,
photo-decoloring agents and photo-discoloring agents of dyes,
well-known compounds capable of generating an acid upon irradiation
with an actinic ray or a radiation that are used in the process of
micro-resist and the like, and the mixtures of these compounds can
be optionally used.
For example, diazonium salt, phosphonium salt, sulfonium salt,
iodonium salt, imidosulfonate, oximesulfonate, diazodisulfone,
disulfone, and o-nitrobenzyl sulfonate are exemplified as
photo-acid generators.
Further, compounds obtained by introducing a group or a compound
capable of generating an acid upon irradiation with an actinic ray
or a radiation to the main chain or the side chain of polymers, for
example, the compounds disclosed in U.S. Pat. No. 3,849,137, German
Patent 3,914,407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263,
JP-A-63-146038, JP-A-63-163452, JP-A-62-153853 and JP-A-63-146029
can be used as photo-acid generators.
The compounds generating an acid by the action of lights as
disclosed in U.S. Pat. No. 3,779,778, EP-126712 can also be
used.
As the compounds decomposable upon irradiation with actinic ray or
radiation and generating an acid that can be used in the invention,
the compounds represented by the following formulae (ZI), (ZII) and
(ZIII) can be exemplified as preferred compounds.
##STR00033##
In formula (ZI), R.sub.201, R.sub.202 and R.sub.203 each represents
an organic group.
X.sup.- represents a non-nucleophilic anion, preferably a sulfonate
anion, a carboxylate anion, bis(alkylsulfonyl)amide anion,
tris(alkylsulfonyl)methide anion, BF.sub.4.sup.-, PF.sub.6.sup.-
and SbF.sub.6.sup.- are exemplified, and preferred anions are
organic anions having a carbon atom.
As preferred anions, organic anions shown below are
exemplified.
##STR00034## wherein R.sub.c1 represents an organic group.
As the organic group represented by R.sub.c1, an organic group
having from 1 to 30 carbon atoms is exemplified, preferably an
alkyl group, a cycloalkyl group, an aryl group, or a group obtained
by linking any of these groups via a linking group, e.g., a single
bond, --O--, --CO.sub.2--, --S--, --SO.sub.3-- or
--SO.sub.2N(Rd.sub.1)-- can be exemplified.
Rd.sub.1 represents a hydrogen atom or an alkyl group.
Rc.sub.3, Rc.sub.4 and Rc.sub.5 each represents an organic
group.
As the preferred organic groups represented by Rc.sub.3, Rc.sub.4
and Rc.sub.5, the same groups as the organic groups exemplified as
preferred organic groups represented by Rc.sub.1 can be
exemplified, and a perfluoroalkyl group having from 1 to 4 is most
preferred.
Rc.sub.3 and Rc.sub.4 may be bonded to each other to form a
ring.
The group formed by bonding Rc.sub.3 and Rc.sub.4, an alkylene
group and an arylene group are exemplified, and a perfluoroalkylene
group having from 2 to 4 carbon atoms is preferred.
The most preferred organic groups represented by R.sub.c1,
R.sub.c3, R.sub.c4 and R.sub.c5 are an alkyl group substituted with
a fluorine atom or a fluoroalkyl group on the 1-position, and a
phenyl group substituted with a fluorine atom or a fluoroalkyl
group. When the acid-generating compound is substituted with a
fluorine atom or a fluoroalkyl group, the acidity of an acid
generated by photo-irradiation increase to thereby improve
sensitivity.
The carbon atoms of the organic groups represented by R.sub.201,
R.sub.202 and R.sub.203 are generally from 1 to 30, preferably from
1 to 20.
Two of R.sub.201, R.sub.202 and R.sub.203 may be bonded to form a
cyclic structure, and an oxygen atom, a sulfur atom, an ester bond,
an amido bond and a carbonyl group may be contained in the ring. As
the group formed by bonding two of R.sub.201, R.sub.202 and
R.sub.203, an alkylene group (e.g., a butylene group, a pentylene
group) can be exemplified.
As the specific examples of the organic groups represented by
R.sub.201, R.sub.202 and R.sub.203, the corresponding groups in the
later-described compounds represented by formula (ZI-1), (ZI-2) or
(ZI-3) can be exemplified.
A compound represented by formula (ZI) may be a compound having a
plurality of structures represented by formula (ZI). For instance,
compound (ZI) may be a compound having a structure that at least
one of R.sub.201, R.sub.202 and R.sub.203 of a compound represented
by formula (ZI) is bonded to at least one of R.sub.201, R.sub.202
and R.sub.203 of another compound represented by formula (ZI).
The following compounds (Z1-1), (Z1-2) and (Z1-3) can be
exemplified as more preferred components (ZI).
Compound (Z1-1) is a compound of formula (ZI) of the case where at
least one of R.sub.201, R.sub.202 and R.sub.203 represents an aryl
group, that is, an arylsulfonium compound having arylsulfonium as
the cation.
All of R.sub.201, R.sub.202 and R.sub.203 of the arylsulfonium
compound may be aryl groups, or a part of R.sub.201, R.sub.202 and
R.sub.203 may be an aryl group and the remainder may be an alkyl
group or a cycloalkyl group.
As the arylsulfonium compounds, e.g., a triarylsulfonium compound,
a diarylalkylsulfonium compound, an aryldialkyl-sulfonium compound,
a diarylcycloalkylsulfonium compound, and an
aryldicycloalkylsulfonium compound are exemplified.
As the aryl groups of the arylsulfonium compound, an aryl group,
e.g., a phenyl group and a naphthyl group, and a hetero-aryl group,
e.g., an indole residue and a pyrrole residue, are preferred, and
the more preferred groups are a phenyl group and an indole residue.
When the arylsulfonium compound has two or more aryl groups, these
two or more aryl groups may be the same or different.
The alkyl group that the arylsulfonium compound has according to
necessity is preferably a straight chain or branched alkyl group
having from 1 to 15 carbon atoms e.g., a methyl group, an ethyl
group, a propyl group, an n-butyl group, a sec-butyl group and a
t-butyl group can be exemplified.
The cycloalkyl group that the arylsulfonium compound has according
to necessity is preferably a cycloalkyl group having from 3 to 15
carbon atoms, e.g., a cyclopropyl group, a cyclobutyl group and a
cyclohexyl group can be exemplified.
The aryl group, alkyl group and cycloalkyl group represented by
R.sub.201, R.sub.202 and R.sub.203 may have a substituent, e.g., an
alkyl group (e.g., having from 1 to 15 carbon atoms), a cycloalkyl
group (e.g., having from 3 to 15 carbon atoms), an aryl group
(e.g., having from 6 to 14 carbon atoms), an alkoxyl group (e.g.,
having from 1 to 15 carbon atoms), a halogen atom, a hydroxyl
group, and a phenylthio group are exemplified as the substituents.
The preferred substituents are a straight chain or branched alkyl
group having from 1 to 12 carbon atoms, a cycloalkyl group having
from 3 to 12 carbon atoms, and an alkoxyl group having from 1 to 12
carbon atoms, and the most preferred substituents are an alkyl
group having from 1 to 4 carbon atoms and an alkoxyl group having
from 1 to 4 carbon atoms. The substituent may be substituted on any
one of three of R.sub.201, R.sub.202 and R.sub.203, or may be
substituted on all of three. When R.sub.201, R.sub.202 and
R.sub.203 each represents an aryl group, it is preferred that the
substituent be substituted on the p-position of the aryl group.
Compound (ZI-2) is described below.
Compound (ZI-2) is a compound of the case of formula (ZI) in which
R.sub.201 to R.sub.203 each represents an organic group not
containing an aromatic, ring. The aromatic ring also includes an
aromatic ring containing a hetero atom.
The organic groups not containing an aromatic ring represented by
R.sub.201 to R.sub.203 generally have from 1 to 30 carbon atoms,
preferably from 1 to 20 carbon atoms.
R.sub.201 to R.sub.203 each preferably represents an alkyl group, a
cycloalkyl group, an allyl group, or a vinyl group, more preferably
a straight chain, branched or cyclic 2-oxoalkyl group or
alkoxycarbonylmethyl group, and particularly preferably a straight
or branched 2-oxoalkyl group.
The alkyl group represented by R.sub.201 to R.sub.203 may be either
straight chain or branched, preferably a straight chain or branched
alkyl group having from 1 to 10 carbon atoms (e.g., a methyl group,
an ethyl group, a propyl group, a butyl group, a pentyl group) can
be exemplified, more preferably a straight chain or branched
oxoalkyl group and alkoxycarbonylmethyl group.
The cycloalkyl group represented by R.sub.201 to R.sub.203 is
preferably a cycloalkyl group having from 3 to 10 carbon atoms
(e.g., a cyclopentyl group, a cyclohexyl group, a norbonyl group),
more preferably a cyclic 2-oxoalkyl group.
As the preferred straight chain, branched or cyclic 2-oxoalkyl
group represented by R.sub.201 to R.sub.203, the above alkyl group
and cycloalkyl group having >C.dbd.O at the 2-position can be
exemplified.
As the alkoxyl group in the alkoxycarbonylmethyl group represented
by R.sub.201 to R.sub.203, an alkoxyl group preferably having from
1 to 5 carbon atoms (e.g., a methoxy group, an ethoxy group, a
propoxy group, a butoxy group, a pentoxy group) can be
exemplified.
R.sub.201 to R.sub.203 may further be substituted with a halogen
atom, an alkoxyl group (e.g., having from 1 to 5 carbon atoms), a
hydroxyl group, a cyano group or a nitro group.
Compound (ZI-3) is a compound represented by the following formula
(ZI-3), which compound has a phenacyl-sulfonium salt structure.
##STR00035##
In formula (ZI-3), R.sub.1c, R.sub.2c, R.sub.3c, R.sub.4c and
R.sub.5c each represents a hydrogen atom, an alkyl group, a
cycloalkyl group, an alkoxyl group or a halogen atom.
R.sub.6c and R.sub.7c each represents a hydrogen atom, an alkyl
group or a cycloalkyl group.
R.sub.x and R.sub.y each represents an alkyl group, a cycloalkyl
group, an allyl group or a vinyl group.
Any two or more of R.sub.1c, to R.sub.5c, R.sub.6c and R.sub.7c,
and R.sub.z and R.sub.y may be bonded to each other to form a
cyclic structure.
Z.sub.c.sup.- represents a non-nucleophilic anion, and the same
anions as the non-nucleophilic anion represented by X.sup.- in
formula (ZI) can be exemplified.
The alkyl group represented by R.sub.1c to R.sub.7c may be either
straight chain or branched, e.g., a straight chain or branched
alkyl group having from 1 to 20 carbon atoms, preferably from 1 to
12 carbon atoms (e.g., a methyl group, an ethyl group, a straight
chain or branched propyl group, a straight chain or branched butyl
group, a straight chain or branched pentyl group) can be
exemplified.
As the cycloalkyl groups represented by R.sub.1c to R.sub.7c,
preferably a cycloalkyl group having from 3 to 8 carbon atoms
(e.g., a cyclopentyl group and a cyclohexyl group) can be
exemplified.
The alkoxyl groups represented by R.sub.1c to R.sub.7c may be any
of straight chain, branched and cyclic, e.g., an alkoxyl group
having from 1 to 10 carbon atoms, a straight chain or branched
alkoxyl group having from 1 to 5 carbon atoms (e.g., a methoxy
group, an ethoxy group, a straight chain or branched propoxy group,
a straight chain or branched butoxy group, a straight chain or
branched pentoxy group), a cyclic alkoxyl group having from 3 to 8
carbon atoms (e.g., a cyclopentyloxy group and a cyclohexyloxy
group) can be exemplified.
As the groups formed by bonding any two or more of R.sub.1c to
R.sub.5c, R.sub.6c and R.sub.7c, and R.sub.z and R.sub.y, a
butylene group and a pentylene group can be exemplified. These
cyclic structures may contain an oxygen atom, a sulfur atom, an
ester bond or an amido bond.
It is preferred that any of R.sub.1c to R.sub.5c represents a
straight chain or branched alkyl group, a cycloalkyl group, or a
straight chain, branched or cyclic alkoxyl group, it is more
preferred that the sum total of the carbon atoms of R.sub.1c to
R.sub.5c is from 2 to 15, by which the solubility in a solvent
increases and generation of particles during preservation can be
restrained.
The alkyl group and cycloalkyl group represented by R.sub.x and
R.sub.y have the same meaning as the alkyl group and cycloalkyl
group represented by R.sub.1c to R.sub.7c.
R.sub.x and R.sub.y each preferably represents a 2-oxoalkyl group
or an alkoxycarbonylmethyl group.
As the 2-oxoalkyl group, a group having >C.dbd.O at the
2-position of the alkyl group and cycloalkyl group represented by
R.sub.1c and R.sub.5c.
As the alkoxyl group of the alkoxycarbonylmethyl group, the same
groups as the alkoxyl group represented by R.sub.1c and R.sub.5c,
can be exemplified.
R.sub.x and R.sub.y each preferably represents an alkyl group or a
cycloalkyl group having 4 or more carbon atoms, more preferably an
alkyl group or a cycloalkyl group having 6 or more carbon atoms,
and more preferably an alkyl group or a cycloalkyl group having 8
or more carbon atoms.
In formulae (ZII) and (ZIII), R.sub.204, R.sub.205, R.sub.206 and
R.sub.207 each represents an aryl group, an alkyl group or a
cycloalkyl group. X.sup.- represents a non-nucleophilic anion, and
the same anions as the non-nucleophilic anion represented by
X.sup.- in formula (I) can be exemplified.
The aryl group represented by R.sub.204 to R.sub.207 is preferably
a phenyl group or a naphthyl group, more preferably a phenyl
group.
The alkyl group represented by R.sub.204 to R.sub.207 may be either
straight chain or branched, and preferably a straight chain or
branched alkyl group having from 1 to 10 carbon atoms (e.g., a
methyl group, an ethyl group, a propyl group, a butyl group, a
pentyl group) can be exemplified.
As the cycloalkyl group represented by R.sub.204 to R.sub.207,
preferably a cycloalkyl group having from 3 to 10 carbon atoms
(e.g., a cyclopentyl group, a cyclohexyl group, a norbonyl group)
can be exemplified.
As the substituents that R.sub.204 to R.sub.207 may have, e.g., an
alkyl group (e.g., having from 1 to 15 carbon atoms), a cycloalkyl
group (e.g., having from 3 to 15 carbon atoms), an aryl group
(e.g., having from 6 to 15 carbon atoms), an alkoxyl group (e.g.,
having from 1 to 15 carbon atoms), a halogen atom, a hydroxyl
group, and a phenylthio group can be exemplified.
As the compounds generating an acid upon irradiation with actinic
ray or radiation that can be used in the invention, the compounds
represented by the following formulae (ZIV), (ZV) and (ZVI) can
further be exemplified.
##STR00036##
In formulae (ZIV), (ZV) and (ZI), Ar.sub.3 and Ar.sub.4 each
represents an aryl group.
R.sub.206, R.sub.207 and R.sub.208 each represents an alkyl group,
a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene
group.
Of the compounds generating an acid upon irradiation with actinic
ray or radiation, more preferred compounds are the compounds
represented by formulae (ZI), (ZII) and (ZIII).
Of the compounds generating an acid upon irradiation with actinic
ray or radiation, particularly preferred examples are shown
below.
##STR00037## ##STR00038## ##STR00039## ##STR00040##
##STR00041##
The compounds generating an acid upon irradiation with actinic ray
or radiation can be used as one kind alone or two or more compounds
can be used in combination.
The content of the compounds generating an acid upon irradiation
with actinic ray or radiation in the chemical amplification resist
composition is preferably from 0.1 to 20 mass % based on the total
solids content of the resist composition, more preferably from 0.5
to 18 mass %, and still more preferably from 1.0 to 15 mass %.
[3] A Compound Having a Fluorine Atom and a Hydroxyl Group, and a
pKa Value of from 4 to 15 (Component (C)):
The chemical amplification resist composition in the invention
contains a compound having a fluorine atom and a hydroxyl group,
and a pKa value of from 4 to 15 (hereinafter also referred to as
"component (C)").
pKa is an equilibrium constant of ionization equilibrium of an
acid, and shows the intensity of acid. The smaller the value, the
stronger is the acid.
In general, when acid HA is in the state of ionization equilibrium,
the ionization equilibrium is shown by the following equation (1),
and the pKa value is given by the following equation (2).
##STR00042##
The pKa value can be computed by an analysis software of chemical
structure, [ACD 5.0] (URL:http://www.acdlabs.com, by Advanced
Chemistry Development Inc.), and the pKa value in the invention is
a value computed according to the software.
The range of pKa of component (C) is from 4 to 15, preferably from
4.5 to 14, and more preferably from 5 to 13.5.
Component (C) is preferably a compound having a molecular weight of
1,500 or less.
Component (C) is preferably a compound represented by the following
formula (FAD-I), (FAD-II) or (FAD-III) (hereinafter also referred
to as component (Ca)).
##STR00043##
In formulae (FAD-I) to (FAD-III), R.sub.a101, R.sub.a102,
R.sub.a103 and R.sub.a104 each represents a hydrogen atom, an alkyl
group, an alicyclic alkyl group, an alkoxyl group, an acyl group or
an acyloxy group.
A.sub.a101, represents a perfluoroalkylene group or a
perfluorocycloalkylene group.
R.sub.a105 may be the same or different when a plurality of
R.sub.a105 are present, and each represents a fluorine atom or a
perfluoroalkyl group.
n represents 1 or 2, and n+m=6.
A.sub.a102 represents a single bond or a divalent linking
group.
R.sub.a106, which may be the same or different, each represents a
fluorine atom or a perfluoroalkyl group.
The alkyl group represented by R.sub.a101, to R.sub.a104 in formula
(FAD-I) is preferably a straight chain or branched alkyl group,
e.g., a methyl group, an ethyl group, a propyl group, an n-butyl
group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl
group, a heptyl group, an octyl group, a nonyl group, a decyl
group, a undecyl group, a dodecyl group, a tridecyl group and a
tetradecyl group can be exemplified.
The alicyclic alkyl group represented by R.sub.a101, to R.sub.a104
is preferably an alicyclic alkyl group having from 3 to 30 carbon
atoms, e.g., an adamantyl group, a noradamantyl group, a decalin
group, a tricyclodecanyl group, a tetracyclododecanyl group, a
norbornyl group, a cedrol group, a cyclopropyl group, a cyclopentyl
group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group,
a cyclodecanyl group, a cyclododecanyl group, a tetrahydrofuranyl
group, a tetrahydrothienyl group, and a tetrahydropyranyl group can
be exemplified. The alicyclic alkyl group represented by R.sub.a101
to R.sub.a104 may have a hetero atom and a functional group in the
ring.
The alkoxyl group represented by R.sub.a101 to R.sub.a104 may be an
alkyloxy group or a cycloalkyloxy group. The alkyl group in the
alkoxyl group represented by R.sub.a101 to R.sub.a104 is preferably
a straight chain or branched alkyl group having from 1 to 30 carbon
atoms, e.g., a methyl group, an ethyl group, a propyl group, an
n-butyl group, a sec-butyl group, a t-butyl group, a pentyl group,
a hexyl group, a heptyl group, an octyl group, a nonyl group, a
decyl group, a undecyl group, a dodecyl group, a tridecyl group and
a tetradecyl group can be exemplified. The cycloalkyl group in the
alkoxyl group represented by R.sub.a101 to R.sub.a104 is preferably
a cycloalkyl group having from 3 to 30 carbon atoms, e.g., a
cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an
adamantyl group, a norbonyl group and a boronyl group can be
exemplified.
The acyl group represented by R.sub.a101, to R.sub.a104 is
preferably an acyl group having from 1 to 10 carbon atoms, e.g., an
acetyl group, an ethylcarbonyl group and a propylcarbonyl group can
be exemplified.
The acyloxy group represented by R.sub.a101 to R.sub.a104 is
preferably an acyloxy group having from 1 to 10 carbon atoms, e.g.,
an acetoxy group and an ethylcarbonyloxy group can be
exemplified.
The perfluoroalkylene group represented by A.sub.a101 is preferably
a straight chain or branched perfluoroalkylene group having from 1
to 15 carbon atoms, which may have a hetero atom. The
perfluorocycloalkylene group represented by A.sub.a101 is
preferably a perfluorocycloalkylene group having from 3 to 15
carbon atoms, which may have a hetero atom.
The specific examples of the perfluoroalkylene group and the
perfluorocycloalkylene group represented by A.sub.a101 are shown
below, but the invention is not limited thereto.
##STR00044##
The compound represented by formula (FAD-I) is preferably
represented by the following formula (FAD-Ia).
HO--CH.sub.2-A.sub.a101-CH.sub.2--OH (FAD-Ia)
In formula (FAD-Ia), A.sub.a101, represents a perfluoroalkylene
group or a perfluorocycloalkylene group.
The specific examples of the compounds represented by formula
(FAD-Ia) are shown below, but the invention is not limited
thereto.
##STR00045## ##STR00046##
The perfluoroalkyl group represented by R.sub.a105 in formula
(FAD-II) is preferably a perfluoroalkyl group having from 1 to 20
carbon atoms, e.g., a trifluoromethyl group, a pentafluoroethyl
group, a perfluoro-n-propyl group and a perfluoroisopropyl group
can be exemplified.
The specific examples of the compounds represented by formula
(FAD-II) are shown below, but the invention is not limited
thereto.
##STR00047##
As the divalent organic group represented by formula A.sub.a102 in
formula (FAD-III), single groups and groups bonding two or more
groups of an alkylene group, an ether group, a thioether group, a
carbonyl group, an ester group, an amido group, a sulfonyl group, a
sulfonamido group, a urethane group and a urea group can be
exemplified. The alkylene group may have a substitutent, e.g., a
fluorine atom.
As the perfluoroalkyl group represented by R.sub.a106, the same
groups as the perfluoroalkyl group represented by R.sub.a105 can be
exemplified.
The specific examples of the compounds represented by formula
(FAD-III) are shown below, but the invention is not limited
thereto.
##STR00048##
The compound represented by formula (FAD-I) can be synthesized by a
reduction reaction with the corresponding ketone compound as a
starting material, and converting the ketone to alcohol, as
described in Jikken Kagaku Koza (Experimental Chemistry Course),
4.sup.th Ed., Vol. 20, pp. 1 to 27. Alternatively, the compound can
be synthesized by a substitution reaction with the corresponding
diiodide, dibromide or dichloride as a starting material, and
converting the halogen atoms other than the fluorine atom to
alcohol, as described in Jikken Kagaku Koza, 4.sup.th Ed., Vol. 20,
pp. 49 to 67.
The compound represented by formula (FAD-II) and the compound
represented by formula (FAD-III) can be synthesized by a
substitution reaction with corresponding diiodide, dibromide or
dichloride as a starting material, and converting the halogen
elements other than the fluorine atom to alcohol, as described in
Jikken Kagaku Koza, 4.sup.th Ed., Vol. 20, pp. 114 to 121. Further,
various compounds are put on the market from Wako Pure Chemical
Industries, Sigma Aldrich Japan K. K., A Z max Co., etc., and so
commercially available.
Compounds of components (C) and (Ca) can be used as one kind alone
or in combination of two or more compounds. The content of the
compounds of components (C) and (Ca) in a chemical amplification
resist composition is preferably from 0.05 to 10.0 mass % based on
the solids content of the composition, more preferably from 0.07 to
8.0 mass %, and still more preferably from 0.10 to 7.0 mass %.
[4] A Nitrogen-Containing Basic Compound (Component (E)):
It is preferred for the chemical amplification resist composition
in the invention to contain a nitrogen-containing basic compound
(component (E)). As the nitrogen-containing basic compound
(component (E)), organic amine, basic ammonium salt and basic
sulfonium salt are used, and it is sufficient to use compounds that
do not deteriorate sublimation and resist performances.
Of these nitrogen-containing basic compounds, organic amine is
preferred for being excellent in imaging property.
Basic compounds disclosed in the following patents can be used in
the invention, e.g., JP-A-63-149640, JP-A-5-249662, JP-A-5-127369,
JP-A-5-289322, JP-A-5-249683, JP-A-5-289340, JP-A-5-232706,
JP-A-5-257282, JP-A-6-242605, JP-A-6-242606, JP-A-6-266100,
JP-A-6-266110, JP-A-6-317902, JP-A-7-120929, JP-A-7-146558,
JP-A-7-319163, JP-A-7-508840, JP-A-7-333844, JP-A-7-219217,
JP-A-7-92678, JP-A-7-28247, JP-A-8-22120, JP-A-8-110638,
JP-A-8-123030, JP-A-9-274312, JP-A-9-166871, JP-A-9-292708,
JP-A-9-325496, JP-T-7-508840 (the term "JP-T" as used herein means
a published Japanese translation of a PCT patent application), U.S.
Pat. Nos. 5,525,453, 5,629,134, and 5,667,938.
As preferred nitrogen-containing basic compounds, e.g.,
1,5-diazabicyclo[4.3.0]-5-nonene,
1,8-diazabicyclo[5.4.0]-7-undecene, 1,4-diazabicyclo[2.2.2]octane,
4-dimethylamino-pyridine, 1-naphthylamine, piperidine,
hexamethylene-tetramine, imidazoles, hydroxypyridines, pyridines,
4,4'-diaminodiphenyl ether, pyridinium p-toluenesulfonate,
2,4,6-trimethylpyridinium p-toluenesulfonate, tetramethylammonium
p-toluenesulfonate, tetrabutylammonium lactate, triethyl-amine, and
tributylamine are exemplified.
Of these compounds, 1,5-diazabicyclo[4.3.0]-5-nonene,
1,8-diazabicyclo[5.4.0]-7-undecene, 1,4-diazabicyclo-[2.2.2]octane,
4-dimethylaminopyridine, 1-naphthylamine, piperidine,
hexamethylenetetramine, imidazoles, hydroxy-pyridines, pyridines,
4,4'-diaminodiphenyl ether, organic amines such as triethylamine
and tributylamine are preferred.
The content of nitrogen-containing basic compounds is generally
from 0.001 to 10 mass parts per 100 mass parts of the chemical
amplification resist composition (solids content), preferably from
0.001 to 5 mass parts, and more preferably from 0.001 to 0.5 mass
parts.
[5] Fluorine and/or Silicon Surfactants (Component (F)):
It is preferred for the chemical amplification resist composition
in the invention to further contain either one or two or more of
fluorine and/or silicon surfactants (a fluorine surfactant, a
silicon surfactant, a surfactant containing both a fluorine atom
and a silicon atom).
By containing surfactant (F), it becomes possible for the chemical
amplification resist composition in the invention to provide a
resist pattern excellent in sensitivity and resolution, and low in
defects in adhesion and development in using an exposure light
source of 250 nm or lower, in particular, 220 nm or lower.
These surfactants (F) are disclosed, e.g., in JP-A-62-36663,
JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540,
JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988,
JP-A-2002-277862, U.S. Pat. Nos. 5,405,720, 5,360,692, 5,529,881,
5,296,330, 5,436,098, 5,576,143, 5,294,511 and 5,824,451. The
following commercially available surfactants can also be used as
they are.
As the fluorine or silicon surfactants usable in the invention,
Eftop EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.),
Fluorad FC 430 and 431 (manufactured by Sumitomo 3M Limited),
Megafac F171, F173, F176, F189 and R08 (manufactured by Dainippon
Ink and Chemicals Inc.), Sarfron S-382, SC101, 102, 103, 104, 105
and 106 (manufactured by ASAHI GLASS CO., LTD.), and Troy Sol S-366
(Troy Chemical Co., Ltd.) are exemplified. In addition,
polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical
Co., Ltd.) can also be used as a silicon surfactant.
As surfactants, in addition to the above-shown well-known
surfactants, surfactants using polymers having fluoro-aliphatic
groups derived from fluoro-aliphatic compounds manufactured by a
telomerization method (also called a telomer method) or an
oligomerization method (also called an oligomer method) can be
used. Fluoro-aliphatic compounds can be synthesized by the method
disclosed in JP-A-2002-90991.
As polymers having fluoro-aliphatic groups, copolymers of monomers
having fluoro-aliphatic groups and (poly(oxy-alkylene))acrylate
and/or (poly(oxyalkylene))methacrylate are preferred, and these
copolymers may be irregularly distributed or may be block
copolymerized. As the poly-(oxyalkylene) groups, a
poly(oxyethylene) group, a poly-(oxypropylene) group and
poly(oxybutylene) group are exemplified. Further, the polymers may
be units having alkylenes different in a chain length in the same
chain length, such as a block combination of poly(oxyethylene and
oxypropylene and oxyethylene), and a block combination of
poly(oxyethylene and oxypropylene). In addition, copolymers of
monomers having fluoro-aliphatic groups and
poly-(oxyalkylene)acrylate (or methacrylate) may be not only
bipolymers but also terpolymers or higher polymers obtained by
copolymerization of monomers having different two or more kinds of
fluoro-aliphatic groups or different two or more kinds of
poly(oxyalkylene)acrylates (or methacrylates) at the same time.
For example, as commercially available surfactants, Megafac F178,
F470, F473, F475, F476 and F472 (manufactured by Dainippon Ink and
Chemicals Inc.) can be exemplified. Further, copolymers of acrylate
(or methacrylate) having a C.sub.6F.sub.13 group and
(poly(oxyalkylene)) acrylate(or methacrylate), copolymers of
acrylate(or methacrylate) having a C.sub.6F.sub.13 group,
(poly(oxyethylene))acrylate (or methacrylate), and
(poly-(oxypropylene))acrylate (or methacrylate), copolymers of
acrylate(or methacrylate) having a C.sub.8F.sub.17 group and
(poly-(oxyethylene))acrylate (or methacrylate), copolymers of
acrylate(or methacrylate) having a C.sub.8F.sub.17 group,
(poly(oxy-ethylene))acrylate (or methacrylate), and
poly(oxypropylene)acrylate (or methacrylate) are exemplified.
The use amount of surfactants (F) is preferably from 0.0001 to 2
mass % to the total amount of the chemical amplification resist
composition (excluding solvents), more preferably from 0.001 to 1
mass %.
[6] Solvent (Component (D)):
In the invention, a chemical amplification resist composition is
prepared by dissolving each component in a solvent. In the
invention, solvents are in a liquid state under the conditions of
25.degree. C., 760 mmHg and have a boiling point of 250.degree. C.
or lower.
The chemical amplification resist composition in the invention can
use as solvent (component D) a single solvent or a mixed solvent.
As the single solvent, alkyl lactate or propylene glycol monoalkyl
ether carboxylate is preferred. As the mixed solvent, mixed
solvents comprising at least two solvents selected from the group
consisting of propylene glycol monoalkyl ether carboxylate,
propylene glycol monoalkyl ether, cyclohexanone and alkyl lactate
are preferred, and mixed solvents comprising at least one kind of
solvent selected from the group consisting of propylene glycol
monoalkyl ether carboxylate and alkyl lactate (also referred to as
the solvent of group A), and at least one kind of solvent selected
from the group consisting of propylene glycol monoalkyl ether and
cyclohexanone (also referred to as the solvent of group B), and a
mixed solvent comprising propylene glycol monoalkyl ether
carboxylate and alkyl lactate are more preferred.
As the propylene glycol monoalkyl ether carboxylate, propylene
glycol monomethyl ether acetate, propylene glycol monomethyl ether
propionate, propylene glycol monoethyl ether acetate, and propylene
glycol monoethyl ether propionate are preferably exemplified.
As the propylene glycol monoalkyl ether, propylene glycol
monomethyl ether and propylene glycol monoethyl ether are
preferably exemplified.
As the alkyl lactate, methyl lactate and ethyl lactate are
preferably exemplified.
The mass ratio of the use amount of the solvent of group A and the
solvent of group B (A/B) is preferably from 90/10 to 15/85, more
preferably from 85/15 to 20/80, and still more preferably from
80/20 to 25/75.
The mass ratio of the use amount of propylene glycol monoalkyl
ether carboxylate and alkyl lactate (propylene glycol monoalkyl
ether carboxylate/alkyl lactate) is preferably from 90/10 to 10/90,
more preferably from 85/15 to 15/85, and still more preferably from
80/20 to 20/80.
In the invention, it is preferred that the solids content of the
composition containing above each component is dissolved in the
above mixed solvent in solid concentration of from 3 to 25 mass %,
more preferably from 5 to 22 mass %, and still more preferably from
7 to 20 mass %.
Preferred combinations of the mixed solvents in the invention are
as follows: Propylene glycol monomethyl ether acetate+propylene
glycol monomethyl ether, Propylene glycol monomethyl ether
acetate+propylene glycol monoethyl ether, Propylene glycol
monomethyl ether acetate+cyclohexanone, Propylene glycol monomethyl
ether acetate+ethyl lactate, Propylene glycol monomethyl ether
acetate+methyl lactate, Propylene glycol monomethyl ether
propionate+propylene glycol monomethyl ether, Propylene glycol
monomethyl ether propionate+propylene glycol monoethyl ether,
Propylene glycol monomethyl ether propionate+cyclohexanone,
Propylene glycol monomethyl ether propionate+ethyl lactate,
Propylene glycol monomethyl ether propionate+methyl lactate,
Propylene glycol monoethyl ether acetate+propylene glycol
monomethyl ether, Propylene glycol monoethyl ether
acetate+propylene glycol monoethyl ether, Propylene glycol
monoethyl ether acetate+cyclohexanone, Propylene glycol monoethyl
ether acetate+ethyl lactate, Propylene glycol monoethyl ether
acetate+methyl lactate, Propylene glycol monoethyl ether
propionate+propylene glycol monomethyl ether, Propylene glycol
monoethyl ether propionate+propylene glycol monoethyl ether,
Propylene glycol monoethyl ether propionate+cyclohexanone,
Propylene glycol monoethyl ether propionate+ethyl lactate,
Propylene glycol monoethyl ether propionate+methyl lactate, Ethyl
lactate+propylene glycol monomethyl ether, Ethyl lactate+propylene
glycol monoethyl ether, Methyl lactate+propylene glycol monomethyl
ether, Methyl lactate+propylene glycol monoethyl ether, Ethyl
lactate+cyclohexanone, and Methyl lactate+cyclohexanone.
Of these combinations, particularly preferred combinations of the
solvents are as follows: Propylene glycol monomethyl ether
acetate+propylene glycol monomethyl ether, Propylene glycol
monomethyl ether acetate+cyclohexanone, Propylene glycol monomethyl
ether acetate+ethyl lactate, and Ethyl lactate+propylene glycol
monomethyl ether.
Other solvents may be added to these mixed solvents. The addition
amount of other solvents is 30 mass parts or less per 100 mass
parts of the mixed solvents of the invention. As other solvents,
e.g., ethylene dichloride, cyclopentanone, methyl ethyl ketone,
.gamma.-butyrolactone, ethylene carbonate, propylene carbonate,
toluene, N,N-dimethylformamide, dimethyl sulfoxide,
N-methylpyrrolidone, and tetrahydrofuran are exemplified.
The chemical amplification resist composition in the invention can
contain, if necessary, a low molecular weight acid-decomposable
compound having a molecular weight of 2,000 or less containing an
acid-decomposable group and being capable of increasing the alkali
solubility by the action of an acid.
As these low molecular weight acid-decomposable compounds, for
example, alicyclic compounds, e.g., acid-decomposable
group-containing cholic acid derivatives, dehydrochloric acid
derivatives, deoxychloric acid derivatives, lithocholic acid
derivatives, ursocholic acid derivatives, and abietic acid
derivatives, and aromatic compounds, e.g., naphthalene derivatives
having an acid-decomposable group as described in Proc. SPIE, 2724,
355 (1996), JP-A-8-15865, U.S. Pat. No. 5,372,912, J. Photopolym.
Sci. Tech., Vol. 10, No. 3, 511 (1997) can be used.
Further, the low molecular weight acid-decomposable
dissolution-inhibiting compounds disclosed in JP-A-6-51519 can be
used in the addition range of not deteriorating the transmission at
220 nm, and 1,2-naphthoquinonediazide compounds can also be
used.
When the low molecular weight acid-decomposable
dissolution-inhibiting compounds are used in the resist composition
in the invention, the content is generally from 0.5 to 50 mass
parts per 100 mass parts (solids content) of the resist
composition, preferably from 0.5 to 40 mass parts, more preferably
from 0.5 to 30 mass parts, and particularly preferably from 0.5 to
20.0 mass parts.
When the low molecular weight acid-decomposable
dissolution-inhibiting compounds are added, not only development
defect is improved but also dry etching resistance is
heightened.
The chemical amplification resist composition in the invention can
further contain, if necessary, a dissolution accelerating compound
in a developing solution, a halation-preventing agent, a
plasticizer, a surfactant, a photo-sensitizer, an adhesion
assistant, a crosslinking agent and a photo-base generator,
etc.
As the examples of the dissolution-accelerating compounds in a
developing solution that can be used in the invention, e.g., low
molecular weight compounds having a molecular weight of 1,000 or
less, such as compounds having two or more phenolic hydroxyl
groups, compounds having one or more naphthols, e.g., 1-naphthol,
or carboxyl groups, carboxylic anhydride, sulfonamide compounds and
sulfonylimide compounds as disclosed in JP-A-3-206458 can be
exemplified.
The blending amount of these dissolution-accelerating compounds is
preferably 30 mass % or less based on the total mass (solids
content) of the composition, more preferably 20 mass % or less.
As halation-preventing agents, compounds that absorb efficiently
the radiation irradiated are preferred, and substituted benzenes,
e.g., fluorenone, 9-fluorenone, benzophenone; and polycyclic
aromatic compounds, e.g., anthracene, anthracene-9-methanol,
anthracene-9-carboxyethyl, phenanthrene, perylene and azirene are
exemplified. Polycyclic aromatic compounds are particularly
preferred. These halation-preventing agents exhibit the effect of
the improvement of standing wave by reducing the reflected light
from a substrate and lessening the influence of multiple-reflection
in a resist film.
The resist composition in the invention can contain a
photo-sensitizer for the improvement of acid generating rate by
exposure. As preferred photo-sensitizers, benzophenone,
p,p'-tetramethyldiaminobenzophenone, 2-chlorothioxanthone,
anthrone, 9-ethoxyanthracene, pyrene, phenothiazine, benzyl,
benzoflavin, acetophenone, phenanthrene, benzoquinone,
anthraquinone and 1,2-naphthoquinone can be exemplified, but
photo-sensitizers are not limited thereto. These photo-sensitizers
can also be used as the halation-preventing agents.
The chemical amplification resist composition in the invention is
coated on a prescribed support as follows.
That is, the chemical amplification resist composition is coated on
a substrate (e.g., silicon/silicon dioxide coating) as used in the
manufacture of a precision integrated circuit element by an
appropriate coating method, e.g., with a spinner or a coater, and
heated to form a resist film.
Subsequently, the resist film is subjected to exposure through a
prescribed mask, heating and development. Thus, a good resist
pattern can be obtained. Here, as exposure light, far ultraviolet
rays having wavelengths of 250 nm or less, preferably 220 nm or
less. Specifically, a KrF excimer laser (248 nm), an ArF excimer
laser (193 nm), an F2 excimer layer (157 nm), an X-ray and an
electron beam are exemplified.
As the alkali developer of the chemical amplification resist
composition, alkaline aqueous solutions of inorganic alkalis, e.g.,
sodium hydroxide, potassium hydroxide, sodium carbonate, sodium
silicate, sodium metasilicate and aqueous ammonia, primary amines,
e.g., ethylamine and n-propylamine, secondary amines, e.g.,
diethylamine and di-n-butylamine, tertiary amines, e.g.,
triethylamine and methyldiethylamine, alcohol amines, e.g.,
dimethylethanolamine and triethanolamine, quaternary ammonium
salts, e.g., tetramethylammonium hydroxide and tetraethylammonium
hydroxide, and cyclic amines, e.g., pyrrole and piperidine, can be
used.
An appropriate amount of alcohols and surfactants may be added to
these alkaline aqueous solutions.
The alkali concentration of alkali developers is generally from 0.1
to 20 mass %.
The pH of alkali developers is generally from 10.0 to 15.0.
EXAMPLE
The invention will be described more specifically with referring to
examples, but the invention is not limited thereto.
Synthesis Example 1
Synthesis of Resin (1)
2-Methyl-2-adamantyl methacrylate and butyrolactone methacrylate in
proportion of 55/45 (in molar ratio) were dissolved in methyl ethyl
ketone/tetrahydrofuran (5/5) to prepare 100 ml of a solution having
solid concentration of 20 mass %. As a polymerization initiator, 2
mol % of V-65 (manufactured by Wako Pure Chemical Industries Ltd.)
was added to the solution, and the mixed solution was dripped to 10
ml of methyl ethyl ketone heated at 60.degree. C. for 4 hours in a
nitrogen atmosphere. After completion of dripping, the reaction
solution was heated for 4 hours, 1 mol % of V-65 was added again,
and the reaction solution was stirred for 4 hours. After
termination of the reaction, the temperature of the reaction
solution was lowered to room temperature, and the reaction solution
was crystallized in 3 liters of a mixed solvent of distilled
water/isopropyl alcohol (1/1 by mass), thus precipitated resin (1)
having the structure shown below was recovered as white powder.
##STR00049##
The polymer composition ratio found by .sup.13C-NMR was 46/54 from
.sup.13NMR. The weight average molecular weight of the resin
calculated in standard polystyrene equivalent by GPC measurement
was 10,700.
Resins (2) to (23) were synthesized in the same manner as in
Synthesis Example 1.
The structures of resins (2) to (23) are shown below.
##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054##
##STR00055## ##STR00056##
The composition ratio and the weight average molecular weight of
each of resins (2) to (23) are shown in Table 1 below. (The
repeating units 1, 2, 3 and 4 mean the order from the left side of
the structural formulae.)
TABLE-US-00001 TABLE 1 Repeating Repeating Repeating Repeating
Repeating Unit 1 Unit 2 Unit 3 Unit 4 Unit 5 Molecular Resin (mol
%) (mol %) (mol %) (mol %) (mol %) Weight 2 41 40 19 -- -- 11,000 3
35 45 20 -- -- 10,000 4 38 39 23 -- -- 10,500 5 35 35 18 12 --
11,500 6 38 30 21 11 -- 12,500 7 21 25 35 19 -- 12,000 8 18 22 35
15 10 12,500 9 35 48 17 -- -- 11,500 10 32 35 22 11 -- 10,000 11 33
39 22 6 -- 9,500 12 35 43 22 -- -- 12,000 13 38 42 20 -- -- 11,500
14 33 45 22 -- -- 11,000 15 31 41 19 9 -- 12,500 16 36 36 18 10 --
9,500 17 34 48 18 -- -- 11,000 18 32 45 23 -- -- 10,500 19 48 28 18
6 -- 9,500 20 42 42 16 -- -- 9,500 21 28 38 24 10 -- 10,000 22 38
31 19 12 -- 10,500 23 25 38 29 8 -- 13,000
Examples 1 to 39 and Comparative Examples 1 to 3
Preparation and Evaluation of Chemical Amplification Resist
Composition:
The chemical amplification resist compositions in Examples 1 to 39
and Comparative Examples 1 to 3 were prepared by blending 1.03 g of
the resin, 0.00035 mol of the acid generator, 16.5 mg of the
compound of component (C), 0.00010 mol of the nitrogen-containing
basic compound, and 100 ppm of the total composition of the
surfactant, as shown in Table 2 below. Each composition was
dissolved in the solvent shown in Table 2 so that the solids
content became 10 mass %, and filtered through a micro-filter of
0.1 .mu.m meshes.
TABLE-US-00002 TABLE 2 Nitrogen- Containing Number of Pattern Acid
Component (C) Basic Development Collapse Ex. No. Resin Generator
(pKa) Compound Surfactant Solvent Defect (nm) Prof- ile Ex. 1 1 z3
FAD-Ia-1 (12.83) N-5 W-2 S-1 2 61 .smallcircle. Ex. 2 1 z3 FAD-Ia-2
(12.68) N-5 W-2 S-1 5 65 .smallcircle. Ex. 3 1 z3 FAD-Ia-3 (12.62)
N-5 W-2 S-1 1 63 .smallcircle. Ex. 4 1 z3 FAD-Ia-4 (12.59) N-5 W-2
S-1 3 60 .smallcircle. Ex. 5 1 z3 FAD-Ia-5 (12.59) N-5 W-2 S-1 3 65
.smallcircle. Ex. 6 1 z3 FAD-Ia-6 (12.59) N-5 W-2 S-1 6 62
.smallcircle. Ex. 7 1 z3 FAD-Ia-7 (12.58) N-5 W-2 S-1 2 66
.smallcircle. Ex. 8 1 z3 FAD-Ia-8 (12.86) N-5 W-2 S-1 5 62
.smallcircle. Ex. 9 1 z3 FAD-Ia-9 (12.84) N-5 W-2 S-1 2 61
.smallcircle. Ex. 10 1 z3 FAD-II-1 (5.90) N-5 W-2 S-1 7 69
.smallcircle. Ex. 11 1 z3 FAD-ll-3 (5.50) N-5 W-2 S-1 7 71
.smallcircle. Ex. 12 1 z3 FAD-II-3 (12.62) N-5 W-2 S-2 1 63
.smallcircle. Ex. 13 1 z3 FAD-Ia-3 (12.62) N-5 W-2 S-4 3 72
.smallcircle. Ex. 14 2 z3 FAD-Ia-3 (12.62) N-5 W-2 S-1/S-2 = 5/5 2
61 .smallcircle. Ex. 15 2 z3 FAD-Ia-3 (12.62) N-5 W-2 S-1/S-3 = 6/4
2 60 .smallcircle. Ex. 16 2 z2 FAD-Ia-3 (12.62) N-5 W-2 S-1/S-4 =
7/3 4 63 .smallcircle. Ex. 17 2 z6 FAD-Ia-3 (12.62) N-5 W-2 S-2/S-3
= 6/4 2 65 .smallcircle. Ex. 18 2 z13 FAD-Ia-3 (12.62) N-5 W-2
S-2/S-4 = 7/3 1 62 .smallcircle. Ex. 19 3 z40 FAD-Ia-3 (12.62) N-6
W-1 S-1/S-4 = 7/3 1 62 .smallcircle. Ex. 20 4 z38 FAD-Ia-3 (12.62)
N-1 W-4 S-1/S-4 = 6/4 4 61 .smallcircle. Ex. 21 5 z59 FAD-Ia-3
(12.62) N-3 W-2 S-1/S-4 = 7/3 3 63 .smallcircle. Ex. 22 6 z56
FAD-Ia-3 (12.62) N-4 W-3 S-1/S-4 = 7/3 3 60 .smallcircle. Ex. 23 7
z8 FAD-Ia-3 (12.62) N-4 W-3 S-1/S-4 = 6/4 6 65 .smallcircle. Ex. 24
8 z55 FAD-Ia-3 (12.62) N-6 W-2 S-1/S-4 = 7/3 5 65 .smallcircle. Ex.
25 9 z58 FAD-Ia-3 (12.62) N-7 W-4 S-1/S-4 = 6/4 2 62 .smallcircle.
Ex. 26 10 z14 FAD-Ia-3 (12.62) N-7 W-1 S-1/S-4 = 6/4 4 63
.smallcircle. Ex. 27 11 z16 FAD-Ia-3 (12.62) N-2 W-4 S-1/S-4 = 7/3
2 61 .smallcircle. Ex. 28 12 z56 FAD-Ia-3 (12.62) N-1 W-4 S-1/S-4 =
6/4 1 61 .smallcircle. Ex. 29 13 z56 FAD-Ia-3 (12.62) N-3 W-3
S-1/S-4 = 7/3 2 61 .smallcircle. Ex. 30 14 z58 FAD-Ia-3 (12.62) N-1
W-4 S-1/S-4 = 7/3 4 63 .smallcircle. Ex. 31 15 z14 FAD-Ia-3 (12.62)
N-5 W-4 S-1/S-4 = 6/4 3 64 .smallcircle. Ex. 32 16 z39 FAD-Ia-3
(12.62) N-3 W-2 S-1/S-4 = 6/4 5 62 .smallcircle. Ex. 33 17 z38
FAD-Ia-3 (12.62) N-1 W-1 S-1/S-4 = 7/3 1 63 .smallcircle. Ex. 34 18
z46 FAD-Ia-3 (12.62) N-4 W-1 S-1/S-4 = 6/4 1 62 .smallcircle. Ex.
35 19 z6 FAD-Ia-3 (12.62) N-6 W-3 S-1/S-4 = 7/3 3 61 .smallcircle.
Ex. 36 20 z3 FAD-Ia-3 (12.62) N-4 W-2 S-1/S-4 = 6/4 0 63
.smallcircle. Ex. 37 21 z3 FAD-Ia-3 (12.62) N-2 W-1 S-1/S-4 = 7/3 6
66 .smallcircle. Ex. 38 22 z58 FAD-Ia-3 (12.62) N-4 W-3 S-1/S-4 =
6/4 0 62 .smallcircle. Ex. 39 23 z16 FAD-Ia-3 (12.62) N-7 W-1
S-1/S-4 = 7/3 4 61 .smallcircle. Comp. 1 1 z3 -- N-5 W-2 S-1 23 75
x Comp. 2 10 z14 -- N-7 W-1 S-1/S-4 = 6/4 36 96 .DELTA. Comp. 3 18
z46 -- N-1 W-1 S-1/S-4 = 6/4 31 75 .DELTA.
The abbreviations in Table 2 are as follows.
As the nitrogen-containing basic compounds: N-1:
1,5-Diazabicyclo[4.3.0]-5-nonene N-2:
1,8-Diazabicyclo[5.4.0]-7-undecene N-3: 4-Dimethylaminopyridine
N-4: N,N-Di(2-hydroxyethyl)aniline N-5: Diisopropylaniline N-6:
Tributylamine N-7: Trioctylamine
As the surfactants: W-1: Megafac F176 (fluorine surfactant,
manufactured by Dainippon Ink and Chemicals Inc.) W-2: Megafac R08
(fluorine and silicon surfactant, manufactured by Dainippon Ink and
Chemicals Inc.) W-3: Polysiloxane polymer KP-341 (manufactured by
Shin-Etsu Chemical Co., Ltd.) W-4: Troy Sol S-366 (manufactured by
Troy Chemical Co., Ltd.)
As the solvents: S-1: Propylene glycol monomethyl ether acetate
S-2: Ethyl lactate S-3: Cyclohexanone S-4: Propylene glycol
monomethyl ether
As the compounds of component (C), commercially available products
by AZ max Co. were used.
The pKa values of the compounds of component (C) were computed by
analysis software of chemical structure, [ACD 5.0].
Methods of Evaluation:
(1) Evaluation of the Suppression of Pattern Collapse
An anti-reflecting, film DUV-42 (manufactured by Brewer Science)
was uniformly coated in a thickness of 600 .ANG. on a silicone
substrate treated with hexamethyldisilazane by a spin coater and
dried at 100.degree. C. for 90 seconds on a hot plate, and further
dried by heating at 190.degree. C. for 240 seconds. After that,
each chemical amplification resist composition was coated thereon
by a spin coater and dried at 120.degree. C. for 90 seconds,
whereby a resist film having a thickness of 0.30 .mu.m was formed.
The resist film was subjected to exposure through a mask with an
ArF excimer laser stepper (NA=0.60, 0.60/0.80 Annular Illumination,
manufactured by ISI), and the exposed resist film was heated on a
hot plate at 120.degree. C. for 90 seconds immediately after
exposure. The resist film was further developed with a 2.38 mass %
tetramethylammonium hydroxide aqueous solution at 23.degree. C. for
60 seconds, rinsed with pure water for 30 seconds, and then dried,
thus a line pattern was obtained. The mask pattern of continuous 15
lines of line and space of 1/1 was evaluated. The measurement of
line width was started from the exposure amount to reproduce a mask
pattern of line and space of 1/1 of 0.13 .mu.m, and the time when
at least one line of the most central five lines collapsed by
varying the exposure amount was taken as the starting point of
pattern collapse. The line width just before the starting point of
pattern collapse (the limit to leave the most central five lines
not collapsed) was taken as the critical line width of pattern
collapse.
(2) Evaluation of Development Defect
The number of development defect of the above repeating pattern
obtained in the above evaluation of pattern collapse was measured
with KLA 2112 tester (manufactured by KLA Tencor Japan) (threshold:
12, pixel size: 0.39).
(3) Evaluation of Profile
The rectangular property of each pattern was evaluated by observing
the cross sectional profile of the pattern reproduced a mask
pattern of line and space of 1/1 of 0.13 .mu.m in the evaluation of
the suppressing effect of pattern collapse with a scanning electron
microscope (model S4300, manufactured by Hitachi, Ltd.) on the
conditions of accelerating voltage of 20 kV, emission electric
current of 5 .mu.A, and by 80,000 magnifications. A pattern having
a good rectangular form was graded .smallcircle., a pattern having
a rectangular form of not so good was graded .DELTA., and bad
rectangular form was graded .times..
The results of evaluations are shown in Table 2.
From the results in Table 2, it is apparently seen that the
chemical amplification resist compositions according to the
invention are extremely few in development defect, and excellent in
the suppressing effect of pattern collapse and the profile.
This application is based on Japanese patent applications JP
2004-238040, filed on Aug. 18, 2004, the entire content of which is
hereby incorporated by reference, the same as if set forth at
length.
* * * * *
References